Method for making titanium, zirconium and tin tellurites



United States Patent 'Ofi 3,053,618 Patented Sept. 11, 1962 ice 3,053,618 METHOD FOR MAKING TITANIUM, ZIRCONIUM I AND TIN TELIJURITES Gerhard Bayer, Hinteregg, Zurich, Switzerland, assignor gh owens-lllinois Glass Company, a corporation of 10 No Drawing. Original application Nov. 23, 1960, Ser. No. 7 1,142. Divided and this application Dec. 22, 1961, Ser. No. 167,207

3 Claims. (Cl.23-50) This invention relates to new metal tellurites, and to methods for their preparation.

This application is a division of copending application Serial Number 71,142, 'filed'November 23, 1960.

An object of the present invention is to provide new crystalline compounds, tellurites of titanium, zirconium and tin. Another object of the invention is to provide methods for the production of these new compounds. Still another object of the invention is to provide new ceramic pigments. Other objects of the invention will become apparent from a study of the accompanying disclosure.

According to the present invention, I have now discovered new metal tellurites of the formula powder form; preferably the powders 21330 microns or smaller. The intimately admixed powders are compacted into a cohesive mass, and thereafter heat treatedin anon reducing, usually an oxidizing, atmosphere 5 ,311 Temperatures of firing are from about 600 to about 700 0., usually not above 650 -C. 'The solid-state reaction takes place during the firing, afterwhich'the compound is cooled to room"temperature.

Each of the compounds, TiTe O Z1Ie O and SriTe O was prepared in the manner just described, wherein the *firing temperature-was 'held'fboth at 600 and700 C. for hours in an air atmosphere. The reaction was complete in thesamples prepared at-each-of these temperatures, as shown by X-ray powder diffraction data. Each of these compounds was found to be insoluble in water and dilute "HCI. Each of the compounds was found .to

be stable up to atemperature of about .750-800" C., but

ATe O mmed pycnometncally.

TABLE I X-ray Powder Dzfiractzon Data TiOg-BTGO: SDOz-3T802 Zl'Og-3Te0z 11170 11 III. hkl 11 M 11 III 11 I/I Md 5. 48 3 200 5. 59 3 5. 33 1 4. 475 31 211 4. 575 4. 323 37 4. 13 13 211 3. 87 7 220 3. 952 1 3. 99 2 3. 59 1 220 3. 13 100 222 3. 224 100 3. 234 100 2. 921 100 222 2. 93 19 321 2. 983 18 3. 028 20 2. 704 2 321 2. 738 30 400 2. 793 37 2. 831 33 2. 529 33 400 2. 531 19 411, 330 2. 333 17 2. 337 19 2. 335 8 411, 330 2. 447 11 420 2. 498 5 2. 532 7 2. 232 2 420 2. 342 2 332 2. 380 2 2. 404 2 2. 157 3 332 2. 233 2 422 2. 278 3 2. 303 2 2.033 1 422 2. 151 9 510, 431 2. 191 3 2. 222 10 1. 934 10 510, 431 2.002 4 521 2. 035 3 2. 07 4 1. 848 3 521 1. 933 23 440 1. 975 27 2. 002 23 1. 788 33 440 1. 88 s 530, 433 1. 91 9 1. 943 8 1. 725 3 530, 433 1. 827 3 300, 442 1. 33 3 1. 888 3 1.383 1 300, 442 1. 777 8 311,532 1.81 3 1.838 8 1. 341 3 311,532 1. 734 3 320 1. 735 5 1. 791 4 1. 30 2 320 1. 391 7 541 1. 722 3 1. 748 3 1. 531 4 541 1.352 23 322 1.382 21 1.708 25 1.525 24 322 1. 317 s 331 1. 345 3 1. 371 8 1. 492 3 331 1. 583 3 444 1. 511 4 1. 334 s 1. 43 3 444 1. 7 710, 550 1. 57s 5 1. 303 5 1. 431 2 710, 550, 543 1. 522 2 340 1. 551 4 1. 572 3 1. 403 2 340 1. 491 5 721, 333 1. 519 4 1. 542 4 1. 377 4 721, 333, 552 1. 435 4 342 1. 491 3 1. 513 5 1. 352 2 342 1. 392 8 732, 351 1. 418 5 1. 439 8 1. 285 3 732. 651 1.37 4 800 1.235 4 800 1. 349 5 811 1. 395 2 1. 413 3 1. 243 3 811 1.33 4 830 1. 374 5 1.395 7 1. 227 2 820 1. 311 4 353 1. 354 4 1. 373 5 1. 209 3 353 1. 292 2 822, 330 1. 325 3 1. 34 3 1. 192 2 822, 330

wherein A is selected from the. group conslstmg of T1, Zr Body centered cubic Structure Mmortype (D and Sn. These compounds have very desirable colors, pa e group TI 213 the tltamum compound bemg a bright, lemon-yellow color,

' d z= s s 8 13 the tin compoun a cream yellow, and the ZlICOllllllIl 60 M96 11. 17 IL 325:0- 01 10.118

compound being white. In the compounds both A and Te =g /(;()m 35 1 5, 52 712 are in the +4 valence state. d(exp.)=g.lccm 5.24 5.31

According to the invention, the new compounds can be prepared by mixing powders of T30 with A0 and carrying out a solid-state reaction. To obtain the compounds in substantially pure form, the ratio of the oxides should be substantially 3:1 of TeO to A0 but higher or lower ratios can be employed; however, when so employed the tellurite compounds are diluted with either TeO or A0 as shown by X-ray powder difiraction data 7 on samples prepared at other ratios. In preparing the compounds, the reactants are intimately admixed in finely These new crystalline compounds find particular application as pigments and colorants because of their desirable white and yellow colors. They can be used in ceramic glazes, enamels, paints and dyes. Different yellow shades can be obtained by mixing both yellow compounds in various ratios or by mixing with the white ZrTe O These compounds in powdered form can be incorporated as powders in amounts from, for instance, 0.5 to 10% or ing the present colors, the following illustrates this use for the pigments.

Ingredient: Lbs. TiTe O or SnTe O or ZrTe O 300 Zinc oxid 25 Long oil soya alkyd resin (60% nonvolatile) 480 Mineral spiri 181 Cobalt naphthenate 6% Co) 3 Lead naphthenate (24% Pb) 3 Calcium naphthenate (4% Ca) 2 Total-.. 994

As will be evident to those skilled in the art, various modifications of this invention can be made or followed in the light of the foregoing disclosure and discussion without departing from the spirit and scope of the disclosure or from the scope of the claims.

I claim:

1. A method of making a crystalline oxide compound of the formula ATe O wherein A is selected from the group consisting of Ti, Sn and Zr, by solid-state reaction which comprises intimately admixing powders of A0 and TeO compacting the resulting admixture into a cohesive mass, and heating said mass at a temperature of from about 600 C. up to the temperature at which said compound begins to decompose at an undesirable rate.

2. A method according to claim 1, wherein the temperature is from 600 to 700 C.

3. A method of claim 1, wherein the molar ratio of TeO to A0 is about 3:1.

References Cited in the file of this patent UNITED STATES PATENTS Jonker et a1 July 26, 1960 Bither Nov. 14, 1961 OTHER REFERENCES 

1. A METHOD OF MAKING A CRYSTALLINE OXIDE COMPOUND OF THE FORMULA ATE3O8, WHEREIN A IS SELECTED FROM THE GROUP CONSISTING OF TI, SN AND ZR, BY SOLID-STATE REACTION WHICH COMPRISES INTIMATELY ADMIXING POWDERS OF AO2 AND TEO2, COMPACTING THE RESULTING ADMIXTURE INTO A COHESIVE MASS, AND HEATING SAID MASS AT A TEMPERATURE OF FROM ABOUT 600*C. UP TO THE TEMPERATURE AT WHICH SAID COMPOUND BEGINS TO DECOMPOSE AT AN UNDESIRABLE RATE. 